Crystal structures of (2E) 1 (3 bromo­thio­phen 2 yl) 3 (2 meth­­oxy­phen­yl)prop 2 en 1 one and (2E) 1 (3 bromo­thio­phen 2 yl) 3 (3,4 di­meth­­oxy­phen­yl)prop 2 en 1 one

research communications

Acta Cryst.(2015).E71, 965–971 doi:10.1107/S2056989015013420

965

Received 23 June 2015 Accepted 13 July 2015

Edited by P. C. Healy, Griffith University, Australia

†

Keywords:crystal structure; bromothiophene; methoxyphenylprop-2-en-1-one; molecular conformation; nearly coplanar molecules; C— H interactions;–sacking interactions

CCDC references:1412491; 1412490 Supporting information:this article has supporting information at journals.iucr.org/e

Crystal structures of (2

E

)-1-(3-bromothiophen-2-yl)-3-(2-methoxyphenyl)prop-2-en-1-one and (2

E

)-1-(3-

bromothiophen-2-yl)-3-(3,4-dimethoxyphenyl)-prop-2-en-1-one

Vasant S. Naik,aVenkataraya Shettigar,b Tyler S. Berglin,cJillian S. Coburn,c Jerry P. Jasinskic* and Hemmige S. Yathirajand

a_{Department of Physics, Government First Grade College, Kumta 581 343, India, Research and Development Centre,}

Bharathiar University, Coimbatore 641 046, India,b_{Department of Physics, Gokhale Centenary College, Ankola 581 314,}

India, Research and Development Centre, Bharathiar University, Coimbatore 641 046, India,c_{Department of Chemistry,}

Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, andd_{Department of Studies in Chemistry, University}

of Mysore, Manasagangotri, Mysuru 570 006, India. *Correspondence e-mail: [email protected]

In the molecules of the title compounds, (2E )-1-(3-bromo-thiophen-2-yl)-3-(2-methoxyphenyl)prop-2-en-1-one, C14H11BrO2S, (I), which crystallizes in the

space groupP1 with four independent molecules in the asymmetric unit (Z0_{= 8),}

and (2E)-1-(3-bromothiophen-2-yl)-3-(3,4-dimethoxyphenyl)prop-2-en-1-one, C15H13BrO3S, (II), which crystallizes withZ0 = 8 in the space group I2/a, the

non-H atoms are nearly coplanar. The molecules of (I) pack with inversion symmetry stacked diagonally along the a-axis direction. Weak C—H Br intramolecular interactions in each of the four molecules in the asymmetric unit are observed. In (II), weak C—H O, bifurcated three-center intermolecular interactions forming dimers along with weak C—H and – stacking interactions are observed, linking the molecules into sheets along [001]. A weak C—H Br intramolecular interaction is also present. There are no classical hydrogen bonds present in either structure.

1. Chemical context

Chalcones are known for their interesting pharmacological activities (Di Carloet al., 1999). A review on the bioactivities of chalcones has been published (Dimmock et al., 1999). Chalcones and their heterocyclic analogs as potential anti-fungal chemotherapeutic agents have been reported (Ople-talova´ & Sedivy´, 1999). Chalcones and flavonoids as anti-tuberculosis agents are reported (Lin et al., 2002). Also, chalcones are recognized material in the photonic industry because of their excellent blue-light transmittance and good crystallizability properties (Gotoet al.1991; Indiraet al., 2002; Sarojiniet al., 2006). 2-Acetyl-3-bromothiophene is one of the well-known bio-active intermediates, and chalcones of 2-acetyl-3-bromothiophene exhibit promising anti-inflamma-tory, analgesic and antibacterial activities (Ashalatha, et al.

2009).

Here we report the crystal structures of two new chalcones, namely (2E )-1-(3-bromo-2-thiophen-2-yl)-3-(2-methoxyphen-yl)prop-2-en-1-one, C14H11BrO2S, (I) (Fig. 1) and (2E

)-1-(3- bromo-2-thiophen-2-yl)-3-(3,4-dimethoxyphenyl)prop-2-en-1-one, C15H13BrO3S, (II) (Fig. 2). Compounds (I) and (II) are of

the general typePC3H2ORandQC3H2ORwherePrepresents

the 2-methoxyphenyl unit in (I), Q represents the 3,4-dimethoxy unit in (II) and Rthe 3-bromo[thiophenyl unit in (I) and (II). The molecular constitutions of compounds (I) and (II) differ only in the number of the methoxyphenyl

tuents, whereby (I) contains only one, P unit, at an ortho

position, and (II) contains two,Q, units at themetaandpara

positions of the phenyl ring.

2. Structural commentary

The structure of C14H11BrO2S, (I), has triclinic (P1) symmetry,

while in (II), C15H13BrO3S, it crystallizes in the monoclinic,I2/

aspace group. In (I), four independent molecules (A,B,C,D) crystallize in the asymmetric unit (Z0_{= 8) (Fig. 1), while only}

one molecule (Z0_{= 8) is present in (II) (Fig. 2). A search for}

possible additional crystallographic symmetry or pseudosym-metry in compound (II) (Spek, 2009) produced none, while in compound (I) there was indication of the possibility of either

P1 symmetry with the a-axis halved or the presence ofC2/c

symmetry. Structural solution of the structure in the C2/c

space group after transforming the axes inPLATONgave a negative result, confirming the (P1) symmetry assignment. Refinement of the structure with two independent molecules in the asymmetry unit rather than four also gave a negative result, even though the coordinates for theA/BandC/Dpairs of molecules are related by translation of 0.5 along theaaxis, displaying pseudo symmetry which gaveBalerts incheckCIF

even after many cycles of refinement.

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14H11BrO2S and C15H13BrO3S Acta Cryst.(2015).E71, 965–971

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Figure 1

The molecular structure of title compound (I), C14H11BrO2S, showing the atom-labelling scheme with 30% probability displacement ellipsoids. Figure 2

The molecular structure of title compound (II), C15H13BrO3S, showing

In the molecular structures of both compounds, (I) and (II), the non-H atoms are almost coplanar, as shown by their relevant torsional and dihedral angles (Table 1). In (I), the mean plane of the keto group is twisted slightly out of plane with that of the thiophene ring in the range of 3–4_{and with}

torsion angles in the range of 174–176 _{in each of the four}

molecules (Table 1). The dihedral angle between the mean planes of the phenyl and thiophene rings are in the range of 10–11_{. In (II), the mean plane of the keto group is twisted}

slightly out of plane with that of the thiophene ring by 0.9 (9)_,

with a torsion angle of 178.2 (6)_{, and a dihedral angle}

between the mean planes of the phenyl and thiophene rings of 8.4 (2)_{. In both compounds, bond lengths and angles are in}

normal ranges (Allenet al., 2002).

3. Supramolecular features

The presence of weak C—H Br intramolecular bonds (Table 2) and absence of any direction-specific weak inter-molecular interactions in (I) in contrast to the presence of a variety of weak C—H O, C—H and–intermolecular

interactions in (II) (Table 3) is suggestive of this type of support in describing the slight differences in planarity of the molecules that is observed between the two compounds. The molecules in (I) pack in zigzag layers in (010) (Fig. 3). Within the asymmetric unit, short O—S intermolecular contacts aligned between each molecule pair [S1D O2A= 3.14 (1), O2C S1A = 3.13 (5), S1C O2B= 3.13 (8), O2D S1B = 3.14 (1) A˚ ] are also observed (Fig. 4). In (II), weak C5— H5 O2 and C5—H5 O3 interactions display bifurcated three-center character, forming dimers in layers along [001] (Fig. 5). Additionally,–stacking interactions occur between the thiophene (S/C2–C5) and phenyl rings (C8–C13) with a ring centroid separation of 3.840 (3)A˚ , and a shortest

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14H11BrO2S and C15H13BrO3S

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Table 1

Selected torsional and dihedral angles (_{) for compounds (I), (II), (III), (IV) and (V).}

Dihedral 1 represents the dihedral angle between the mean planes of the phenyl and thiophene rings, Dihedral 2 represents the dihedral angle between the mean planes of the thiophene ring and the keto unit, and Dihedral 3 represents the dihedral angle between the mean planes of the phenyl ring and the keto unit.

Parameter (I) (II) (III) (IV) (V)

C12A—C11A—C10A—O2A 174.3 (5) C12B—C11B—C10B—O2B 175.8 (5) C12C—C11C—C10C—O2C 174.3 (5) C12D—C11D—C10D—O2D 176.5 (5)

C3—C2—C1—O1 178.2 (6)

C3A—C4A—C5A—O1A 176.5 (7)

C3B—C4B—C5B—O1B 178.2 (8)

C3—C4—C5—O1 161.0 (3)

C2—C1—C5—O5 3.3 (8)

Dihedral 1 11.3 (6)

10.9 (6) 11.3 (6) 11.1 (1)

8.4 (2)

4.9 (7) 12.2 (4)

19.5 (7)

7.1 (8)

Dihedral 2 4.1 (4)

3.4 (9) 3.0 (3) 3.3 (2)

0.9 (9)

2.8 (2) 5.1 (1)

18.6 (3)

4.0 (9)

Dihedral 3 7.4 (3)

7.7 (5) 7.3 (1) 7.6 (6)

9.1 (1)

3.8 (2) 9.8 (9)

10.2 (0)

3.8 (7)

Table 2

Hydrogen-bond geometry (A˚ ,_{) for (I).}

D—H A D—H H A D A D—H A

perpendicular distance from the centroid of one ring to the plane of the other of 3.454 (2) A˚ .

4. Database survey

A search of the Cambridge Structural Database (Version 5.36, last update February 2015: Allen 2002) revealed three closely related (3-bromo-2-thiophen-2-yl)-3-(dimethoxyphenyl)prop-2-en-1-one types of compounds similar to the title compounds in this study and will be referred to as (III) (2E )-1-(3-bromothien-2-yl)-3-phenylprop-2-en-1-one (Butcher et al., 2007d), (IV) (2E )-1-(3-bromo-2-thiophen-2-yl)-3-(4-meth-oxyphenyl)prop-2-en-1-one (Harrison et al., 2006) and (V) (2E )-1-(3-bromo-2-thiophen-2-yl)-3-(2,5-dimethoxyphenyl)-prop-2-en-1-one (Yathirajan et al., 2006) for structural comparisons (Fig. 6).

The crystal structures of some other related chalcones,viz., (2E )-1-(3-bromo-2-thiophen-2-yl)-3-(4-methoxy-2,3,6-tri-methylphenyl)prop-2-en-1-one (Yathirajan et al., 2006a), (2E )-1-(3-bromo-2-thiophen-2-yl)-3-(4,5-dimethoxy-2-nitro-phenyl)prop-2-en-1-one (Yathirajanet al., 2006b), (2E

)-1-(3-968

14H11BrO2S and C15H13BrO3S Acta Cryst.(2015).E71, 965–971

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Figure 3

The molecular packing for compound (I), viewed along the a axis, showing zigzag layers in (010). H atoms not involved in hydrogen bonding and weak intermolecular interactions have been omitted for clarity.

Figure 4

A view of the asymmetric unit in (I), with dashed lines showing short O S intermolecular contacts between each molecule pair [S1D O2A

= 3.14 (1), O2C S1A= 3.13 (5), S1C O2B= 3.13 (8), O2D S1B= 3.14 (1) A˚ ].

Table 3

Hydrogen-bond geometry (A˚ ,_{) for (II).}

D—H A D—H H A D A D—H A

C5—H5 O2i _{0.95 2.52 3.301 (6) 140} C5—H5 O3i 0.95 2.45 3.291 (6) 148 C6—H6 Br1 0.95 2.59 3.361 (5) 139 C14—H14A O1ii 0.98 2.59 3.495 (6) 154

Symmetry codes: (i)x;yþ3 2;zþ

1

2; (ii)x;yþ 1 2;z

1 2.

Figure 5

bromo-2-thienyl)-3-(2,5-dimethoxyphenyl)prop-2-en-1-one (Yathirajan et al., 2006c), 1-(3-bromo-2-thienyl)-3-[4-(di-methylamino)phenyl]prop-2-en-1-one (Butcheret al., 2007a), 1-(3-bromo-2-thienyl)-3-(4-butoxyphenyl)prop-2-en-1-one (Butcheret al., 2007b) and 1-(3-bromo-2-thienyl)-3-(6-meth-oxy-2-naphthyl)prop-2-en-1-one (Butcheret al., 2007c) have also been reported.

Compound (IV) is structurally similar to (I) with the only difference occurring in thePunit with the methoxy group now in the para position on the phenyl ring. Compound (V) is structurally similar to (II) with theQunit now containing the two methoxy groups at the ortho andmeta positions of the

phenyl ring, Compound (III), which crystallized with two independent molecules in the asymmetric unit, is structurally similar to both (I) and (II) except with no methoxy groups on the phenyl ring. TheRunits are structurally identical in all five compounds described here.

A comparison of the supramolecular features of the title compounds (Table 4) suggests that the presence or absence of direction-specific weak intermolecular interactions plays a role in their influence on the small differences in planarity observed and supported by similar types of interactions in closely related compounds. No classical hydrogen bonds are observed in any of the five compounds. All five compounds do display a similar weak C—H Br intramolecular interaction. In (I) and (III) only weak C—H intermolecular inter-actions are observed, while in (IV) only weak C—H O intermolecular interactions are present.

In (II), the weak C5—H5 O2 and C5—H5 O3 inter-actions display bifurcated three-center character, forming dimers in layers along [001]. Additionally, C—H and–

stacking interactions (Table 4) are observed, which help pack the molecules into a two-dimensional network (Fig. 4). In (V), weak C—H O also form bifurcated three-center character in a similar fashion to (II).

5. Synthesis and crystallization

For crystals (I) and (II), the following procedure was used. A solution of 3-bromo-2-acetylthiophene (2.05 g, 0.01 mol) in

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Table 4

Hydrogen bonds and short intermolecular contacts (A˚ ,_{) for compounds (I), (II), (III), (IV) and (V).}

Cg2(I) represents the centroid of the ring C2A–C7A,Cg4(I) represents the centroid of the ring C2B–C7B,Cg6(I) represents the centroid of the ring C2C–C7C,

Cg8(I) represents the centroid of the ring C2D–C7D,Cg1(II) represents the centroid of the ring S1/C2–C5,Cg1(III) represents the centroid of the ring S1A/C1A– C4A,Cg2(III) represents the centroid of the ring C8A–C13A,Cg3(III) represents the centroid of the ring S1B/C1B–C4B.

Compound D—H A D—H H A D A D—H A

(I) C9A—H9A Br1A 0.95 2.68 3.400 (5) 132

C9B—H9B Br1B 0.95 2.68 3.401 (5) 132

C9C—H9C Br1C 0.95 2.68 3.400 (5) 133

C9D—H9D Br1D 0.95 2.68 3.405 (4) 133

C13A—H13A Cg8i _{2.96 3.678 (6) 134}

C13B—H13B Cg6ii _{2.96 3.666 (6) 132}

C13C—H13C Cg4iii _{2.95 3.667 (6) 133}

C13D—H13D Cg2iv 2.94 3.664 (5) 134

(II) C5—H5 O2v _{0.95 2.52 3.301 (6) 140}

C5—H5 O3vi 0.95 2.45 3.291 (6) 147

C14—H14A O1vii _{0.98 2.59 3.495 (6) 154}

C6—H6 Br1 0.95 2.59 3.361 (5) 139

C15—H15B Cg1(II)viii _{2.98 3.734 (7) 135}

(III) C6A—H6AA Br1A 0.95 2.61 3.1367 (3) 137

C6B—H6BA Br1B 0.95 2.68 3.421 (8) 135

C1A—H1A Cg2(III)ix _{2.87 3.566 (8) 131}

C10A—H10A Cg1(III)x

3.00 3.668 (8) 129

C10B—H10B Cg3(III)xi _{2.92 3.659 (8) 135}

(IV) C1—H1 O2xii 0.95 2.54 3.457 (3) 162

C14—H14B O1xiii _{0.98 2.45 3.300 (4) 145}

C6—H6 Br1 0.95 2.73 3.410 (3) 129

(V) C4—H4 O5xiv _{0.96 2.37 3.296 (3) 164}

C17—H17 O5xv 0.98 2.41 3.331 (9) 157

C6—H6 Br1 0.95 2.68 3.394 (7) 133

Symmetry codes: (i) 1x, 1y,z; (ii)x, 1y,z; (iii)x, 1y, 1z; (iv) 1x,1 2+y,

1 2z; (v)x,

3 2y,

1 2+z; (vi)x,

3 2y,

3 2+z; (vii)x,

1 2y,

1 2+z; (viii)

1 2x,

1 2+y,

1 2z; (ix) 1

2+x,y,z; (x)12x, 1y,z; (xi)12+x,y,z; (xii)x,y,1 +z; (xiii)x,12+y, 1z; (xiv) 3x,12+y, 2z; (xv) 1x,12+y, 2z.

Figure 6

methanol (20 ml) was mixed with 2-methoxybenzaldehyde (1.36 g, 0.01 mol) for crystal (I) and 3,4-dimethoxy-benzaldehyde (1.66 g, 0.01 mol) for crystal (II) in methanol (20 ml) in the presence of NaOH (5 ml, 30%) at 283 K. After stirring for four h, the contents of the flask were poured into ice-cold water (250 ml). The resulting crude solid was collected by filtration and dried in a hot-air oven at 323 K. A supersaturated solution was obtained by dissolving the sample in acetone at ambient temperature. The prepared solution was filtered, warmed slightly and allowed to evaporate slowly at room temperature. After several days X-ray quality crystals were obtained by the slow the evaporation technique, m.p.: 367 K for (I) and 405 K for (II).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. In both (I) and (II), all H atoms were located in difference maps. The H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions with C—H distances 0.95 A˚ (aromatic and hetero-aromatic) or 0.98 A˚ (CH3) and withUiso(H) = kUeq(C),

where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C atoms. The maximum residual electron density peaks of 1.17 and0.82 A˚3, for (I), were located at 0.94 and 0.84 A˚ from Br1, respectively. For (II), the maximum residual electron

density peaks of 3.38 and2.20 A˚3_{were located at 0.94 and}

0.84 A˚ from Br1.

Acknowledgements

VSN thanks the Gokhale Centenary College, Ankola, for research facilities. JPJ acknowledges the NSF–MRI program (grant No. 1039027) for funds to purchase the X-ray diffract-ometer.

References

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14H11BrO2S and C15H13BrO3S Acta Cryst.(2015).E71, 965–971

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Table 5

Experimental details.

(I) (II)

Crystal data

Chemical formula C14H11BrO2S C15H13BrO3S

Mr 323.20 353.22

Crystal system, space group Triclinic,P1 Monoclinic,I2/a

Temperature (K) 173 173

a,b,c(A˚ ) 11.2517 (4), 14.5397 (6), 16.7857 (6) 13.4748 (7), 8.3853 (3), 25.0214 (9) ,,(

) 76.561 (3), 89.989 (3), 78.836 (3) 90, 93.957 (4), 90

V(A˚3_{) 2617.44 (17) 2820.4 (2)}

Z 8 8

Radiation type CuK CuK

(mm1_{) 5.70 5.40}

Crystal size (mm) 0.490.440.28 0.320.280.22

Data collection

Diffractometer Agilent Eos Gemini Agilent Eos Gemini

Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2014) Multi-scan (CrysAlis PRO; Agilent, 2014)

Tmin,Tmax 0.353, 1.000 0.726, 1.000

No. of measured, independent and observed [I> 2(I)] reflections

19842, 9990, 4573 5523, 2690, 2399

Rint 0.037 0.026

(sin/ )max(A˚

1_{) 0.614 0.615}

Refinement

R[F2> 2(F2)],wR(F2),S 0.047, 0.168, 1.01 0.074, 0.187, 1.04

No. of reflections 9990 2690

No. of parameters 653 183

H-atom treatment H-atom parameters constrained H-atom parameters constrained

(/)max 0.148 < 0.001

max,min(e A˚

3_{) 1.17,0.82 3.38,2.20}

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supporting information

sup-1

Acta Cryst. (2015). E71, 965-971

supporting information

Acta Cryst. (2015). E71, 965-971 [https://doi.org/10.1107/S2056989015013420]

Crystal structures of (2

E

)-1-(3-bromothiophen-2-yl)-3-(2-methoxyphenyl)-prop-2-en-1-one and (2

E

)-1-(3-bromothiophen-2-yl)-3-(3,4-dimethoxyphenyl)-prop-2-en-1-one

Vasant S. Naik, Venkataraya Shettigar, Tyler S. Berglin, Jillian S. Coburn, Jerry P. Jasinski and

Hemmige S. Yathirajan

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis RED (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(I) (2E)-1-(3-Bromothiophen-2-yl)-3-(2-methoxyphenyl)prop-2-en-1-one

Crystal data

C14H11BrO2S Mr = 323.20

Triclinic, P1

a = 11.2517 (4) Å

b = 14.5397 (6) Å

c = 16.7857 (6) Å

α = 76.561 (3)°

β = 89.989 (3)°

γ = 78.836 (3)°

V = 2617.44 (17) Å3

Z = 8

F(000) = 1296

Dx = 1.640 Mg m−3

Cu Kα radiation, λ = 1.54184 Å Cell parameters from 5217 reflections

θ = 4.6–70.9°

µ = 5.70 mm−1 T = 173 K

Irregular, colourless 0.49 × 0.44 × 0.28 mm

Data collection

Agilent Eos Gemini diffractometer

Radiation source: Enhance (Cu) X-ray Source Detector resolution: 16.0416 pixels mm-1 ω scans

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)

Tmin = 0.353, Tmax = 1.000

19842 measured reflections 9990 independent reflections 4573 reflections with I > 2σ(I)

Rint = 0.037

θmax = 71.3°, θmin = 4.0°

h = −13→8

k = −17→17

l = −20→20

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.047} wR(F2_{) = 0.168} S = 1.01

9990 reflections 653 parameters 0 restraints

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Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(Fo2_{) + (0.0832P)}2_]

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max = 0.148

Δρmax = 1.17 e Å−3

Δρmin = −0.82 e Å−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

Br1C −0.03752 (6) 0.89566 (4) 0.11911 (4) 0.04215 (18) S1C −0.02881 (12) 0.58646 (10) 0.21914 (8) 0.0281 (3) O1C 0.4824 (3) 0.6319 (3) −0.0458 (2) 0.0298 (9) O2C 0.1708 (3) 0.5722 (3) 0.1207 (2) 0.0303 (8) C1C 0.5883 (5) 0.5823 (4) −0.0767 (4) 0.0368 (14)

H1CA 0.5816 0.5987 −0.1368 0.055*

H1CB 0.5953 0.5125 −0.0562 0.055*

H1CC 0.6603 0.6017 −0.0583 0.055*

C2C 0.4461 (4) 0.7277 (4) −0.0760 (3) 0.0198 (10) C3C 0.5054 (4) 0.7849 (4) −0.1346 (3) 0.0268 (11)

H3C 0.5779 0.7567 −0.1561 0.032*

C4C 0.4596 (5) 0.8819 (4) −0.1616 (3) 0.0319 (12)

H4C 0.5019 0.9202 −0.2008 0.038*

C5C 0.3544 (5) 0.9244 (4) −0.1332 (4) 0.0390 (14)

H5C 0.3224 0.9914 −0.1534 0.047*

C6C 0.2948 (5) 0.8678 (4) −0.0741 (3) 0.0306 (12)

H6C 0.2225 0.8976 −0.0534 0.037*

C7C 0.3374 (4) 0.7697 (3) −0.0445 (3) 0.0192 (10) C8C 0.2771 (4) 0.7080 (3) 0.0168 (3) 0.0211 (10)

H8C 0.3168 0.6422 0.0335 0.025*

C9C 0.1732 (4) 0.7324 (3) 0.0525 (3) 0.0231 (10)

H9C 0.1307 0.7975 0.0403 0.028*

C10C 0.1253 (4) 0.6578 (4) 0.1105 (3) 0.0187 (10) C11C 0.0180 (4) 0.6843 (4) 0.1582 (3) 0.0189 (10) C12C −0.0524 (5) 0.7689 (4) 0.1692 (3) 0.0259 (11) C13C −0.1438 (5) 0.7531 (5) 0.2268 (3) 0.0361 (14)

H13C −0.2000 0.8035 0.2416 0.043*

C14C −0.1415 (5) 0.6582 (4) 0.2579 (3) 0.0303 (12)

H14C −0.1961 0.6343 0.2968 0.036*

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O1D 0.9843 (3) 0.6313 (3) −0.0454 (2) 0.0300 (9) O2D 0.6696 (3) 0.5728 (3) 0.1210 (2) 0.0301 (8) C1D 1.0906 (4) 0.5823 (4) −0.0765 (3) 0.0311 (12)

H1DA 1.0727 0.5782 −0.1325 0.047*

H1DB 1.1159 0.5171 −0.0415 0.047*

H1DC 1.1561 0.6181 −0.0767 0.047*

C2D 0.9458 (4) 0.7278 (4) −0.0761 (3) 0.0187 (10) C3D 1.0067 (4) 0.7839 (4) −0.1352 (3) 0.0267 (11)

H3D 1.0781 0.7552 −0.1574 0.032*

C4D 0.9610 (5) 0.8821 (4) −0.1606 (3) 0.0355 (14)

H4D 1.0044 0.9214 −0.1982 0.043*

C5D 0.8523 (5) 0.9244 (4) −0.1322 (3) 0.0357 (13)

H5D 0.8193 0.9910 −0.1533 0.043*

C6D 0.7927 (5) 0.8694 (4) −0.0735 (3) 0.0298 (12)

H6D 0.7204 0.8990 −0.0528 0.036*

C7D 0.8376 (4) 0.7703 (3) −0.0440 (3) 0.0193 (10) C8D 0.7773 (4) 0.7092 (4) 0.0175 (3) 0.0215 (10)

H8D 0.8174 0.6435 0.0348 0.026*

C9D 0.6745 (4) 0.7328 (3) 0.0525 (3) 0.0196 (9)

H9D 0.6321 0.7980 0.0405 0.024*

C10D 0.6254 (4) 0.6576 (4) 0.1104 (3) 0.0191 (10) C11D 0.5194 (4) 0.6847 (3) 0.1587 (3) 0.0184 (9) C12D 0.4472 (4) 0.7684 (4) 0.1688 (3) 0.0236 (10) C13D 0.3574 (4) 0.7535 (4) 0.2272 (3) 0.0303 (12)

H13D 0.3014 0.8039 0.2421 0.036*

C14D 0.3616 (5) 0.6586 (5) 0.2588 (4) 0.0361 (14)

H14D 0.3087 0.6346 0.2990 0.043*

Br1A 0.41043 (6) 0.10433 (4) 0.38081 (4) 0.04188 (19) S1A 0.26463 (11) 0.41362 (9) 0.28077 (7) 0.0270 (3) O1A 0.7996 (3) 0.3677 (3) 0.5461 (2) 0.0306 (9) O2A 0.4566 (3) 0.4277 (3) 0.3799 (2) 0.0295 (8) C1A 0.8804 (5) 0.4168 (4) 0.5775 (3) 0.0350 (13)

H1AA 0.8602 0.4858 0.5509 0.052*

H1AB 0.9640 0.3904 0.5665 0.052*

H1AC 0.8725 0.4080 0.6368 0.052*

C2A 0.8093 (4) 0.2730 (3) 0.5760 (3) 0.0198 (10) C3A 0.8983 (5) 0.2159 (4) 0.6342 (3) 0.0290 (12)

H3A 0.9572 0.2442 0.6550 0.035*

C4A 0.9009 (5) 0.1179 (4) 0.6616 (3) 0.0349 (14)

H4A 0.9623 0.0795 0.7009 0.042*

C5A 0.8147 (5) 0.0747 (4) 0.6324 (4) 0.0365 (13)

H5A 0.8160 0.0078 0.6523 0.044*

C6A 0.7271 (4) 0.1315 (4) 0.5736 (3) 0.0309 (13)

H6A 0.6690 0.1025 0.5528 0.037*

C7A 0.7227 (4) 0.2300 (3) 0.5443 (3) 0.0172 (9) C8A 0.6313 (4) 0.2924 (3) 0.4822 (3) 0.0194 (10)

H8A 0.6386 0.3580 0.4645 0.023*

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H9A 0.5292 0.2020 0.4610 0.024*

C10A 0.4538 (4) 0.3418 (3) 0.3902 (3) 0.0188 (9) C11A 0.3599 (4) 0.3155 (3) 0.3419 (3) 0.0186 (9) C12A 0.3308 (4) 0.2328 (4) 0.3300 (3) 0.0246 (11) C13A 0.2337 (5) 0.2469 (4) 0.2734 (3) 0.0315 (12)

H13A 0.2033 0.1963 0.2585 0.038*

C14A 0.1897 (5) 0.3403 (4) 0.2432 (4) 0.0352 (14)

H14A 0.1229 0.3640 0.2044 0.042*

Br1B −0.08962 (6) 0.10432 (4) 0.38073 (4) 0.04162 (19) S1B −0.23554 (11) 0.41352 (10) 0.28088 (7) 0.0276 (3) O1B 0.2986 (3) 0.3684 (3) 0.5458 (2) 0.0301 (9) O2B −0.0437 (3) 0.4276 (3) 0.3792 (2) 0.0294 (8) C1B 0.3811 (4) 0.4181 (4) 0.5759 (3) 0.0345 (13)

H1BA 0.4638 0.3934 0.5619 0.052*

H1BB 0.3773 0.4075 0.6356 0.052*

H1BC 0.3584 0.4874 0.5507 0.052*

C2B 0.3094 (4) 0.2722 (4) 0.5759 (3) 0.0201 (10) C3B 0.3978 (4) 0.2151 (4) 0.6341 (3) 0.0268 (11)

H3B 0.4570 0.2432 0.6548 0.032*

C4B 0.3999 (5) 0.1186 (4) 0.6617 (3) 0.0353 (14)

H4B 0.4599 0.0806 0.7021 0.042*

C5B 0.3158 (5) 0.0750 (4) 0.6318 (4) 0.0385 (14)

H5B 0.3189 0.0077 0.6507 0.046*

C6B 0.2273 (4) 0.1314 (4) 0.5738 (3) 0.0293 (12)

H6B 0.1688 0.1022 0.5538 0.035*

C7B 0.2222 (4) 0.2305 (3) 0.5441 (3) 0.0199 (10) C8B 0.1314 (4) 0.2912 (3) 0.4831 (3) 0.0206 (10)

H8B 0.1373 0.3572 0.4668 0.025*

C9B 0.0413 (4) 0.2668 (3) 0.4471 (3) 0.0223 (10)

H9B 0.0323 0.2015 0.4586 0.027*

C10B −0.0450 (4) 0.3420 (4) 0.3890 (3) 0.0221 (10) C11B −0.1379 (4) 0.3144 (3) 0.3419 (3) 0.0188 (9) C12B −0.1673 (4) 0.2310 (4) 0.3310 (3) 0.0249 (11) C13B −0.2675 (5) 0.2455 (4) 0.2742 (3) 0.0329 (13)

H13B −0.2993 0.1950 0.2603 0.039*

C14B −0.3121 (5) 0.3430 (4) 0.2419 (3) 0.0358 (14)

H14B −0.3781 0.3675 0.2025 0.043*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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S1B 0.0285 (6) 0.0249 (7) 0.0246 (7) 0.0032 (5) −0.0073 (5) −0.0029 (5) O1B 0.035 (2) 0.0191 (19) 0.034 (2) −0.0066 (15) −0.0118 (16) 0.0001 (15) O2B 0.0334 (19) 0.0164 (18) 0.033 (2) −0.0056 (15) −0.0105 (16) 0.0056 (15) C1B 0.033 (3) 0.032 (3) 0.043 (3) −0.010 (2) −0.008 (2) −0.014 (3) C2B 0.025 (2) 0.022 (3) 0.013 (2) −0.005 (2) 0.0034 (18) −0.0040 (19) C3B 0.026 (3) 0.032 (3) 0.020 (3) −0.001 (2) −0.003 (2) −0.005 (2) C4B 0.032 (3) 0.036 (3) 0.027 (3) 0.000 (2) −0.004 (2) 0.010 (2) C5B 0.037 (3) 0.023 (3) 0.046 (4) −0.002 (2) −0.008 (3) 0.008 (2) C6B 0.030 (3) 0.020 (3) 0.031 (3) −0.004 (2) −0.003 (2) 0.005 (2) C7B 0.021 (2) 0.019 (2) 0.018 (2) −0.0038 (19) 0.0042 (19) −0.0023 (19) C8B 0.026 (2) 0.011 (2) 0.022 (2) −0.0033 (19) 0.003 (2) 0.0003 (18) C9B 0.030 (3) 0.016 (2) 0.018 (2) −0.004 (2) −0.001 (2) 0.0004 (18) C10B 0.027 (2) 0.023 (3) 0.014 (2) −0.004 (2) 0.0019 (19) −0.0002 (19) C11B 0.020 (2) 0.020 (2) 0.015 (2) −0.0024 (19) 0.0049 (17) −0.0011 (18) C12B 0.022 (2) 0.026 (3) 0.025 (3) 0.001 (2) 0.001 (2) −0.007 (2) C13B 0.031 (3) 0.041 (3) 0.031 (3) −0.006 (2) 0.001 (2) −0.019 (3) C14B 0.037 (3) 0.037 (3) 0.030 (3) 0.003 (3) −0.008 (2) −0.011 (3)

Geometric parameters (Å, º)

Br1C—C12C 1.880 (5) Br1A—C12A 1.905 (5)

S1C—C11C 1.721 (5) S1A—C11A 1.722 (4)

S1C—C14C 1.710 (5) S1A—C14A 1.705 (5)

O1C—C1C 1.431 (6) O1A—C1A 1.430 (6)

O1C—C2C 1.348 (6) O1A—C2A 1.334 (6)

O2C—C10C 1.223 (6) O2A—C10A 1.226 (6)

C1C—H1CA 0.9800 C1A—H1AA 0.9800

C1C—H1CB 0.9800 C1A—H1AB 0.9800

C1C—H1CC 0.9800 C1A—H1AC 0.9800

C2C—C3C 1.393 (7) C2A—C3A 1.395 (6)

C2C—C7C 1.418 (6) C2A—C7A 1.420 (6)

C3C—H3C 0.9500 C3A—H3A 0.9500

C3C—C4C 1.371 (7) C3A—C4A 1.386 (8)

C4C—H4C 0.9500 C4A—H4A 0.9500

C4C—C5C 1.364 (8) C4A—C5A 1.399 (8)

C5C—H5C 0.9500 C5A—H5A 0.9500

C5C—C6C 1.395 (7) C5A—C6A 1.391 (7)

C6C—H6C 0.9500 C6A—H6A 0.9500

C6C—C7C 1.384 (7) C6A—C7A 1.392 (7)

C7C—C8C 1.460 (6) C7A—C8A 1.472 (6)

C8C—H8C 0.9500 C8A—H8A 0.9500

C8C—C9C 1.337 (6) C8A—C9A 1.336 (6)

C9C—H9C 0.9500 C9A—H9A 0.9500

C9C—C10C 1.466 (6) C9A—C10A 1.466 (6)

C10C—C11C 1.487 (6) C10A—C11A 1.490 (6) C11C—C12C 1.379 (7) C11A—C12A 1.363 (7) C12C—C13C 1.425 (7) C12A—C13A 1.401 (7)

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C13C—C14C 1.351 (8) C13A—C14A 1.329 (8)

C14C—H14C 0.9500 C14A—H14A 0.9500

Br1D—C12D 1.886 (5) Br1B—C12B 1.875 (5)

S1D—C11D 1.728 (5) S1B—C11B 1.742 (5)

S1D—C14D 1.701 (5) S1B—C14B 1.696 (6)

O1D—C1D 1.433 (5) O1B—C1B 1.439 (6)

O1D—C2D 1.360 (6) O1B—C2B 1.353 (6)

O2D—C10D 1.208 (6) O2B—C10B 1.221 (6)

C1D—H1DA 0.9800 C1B—H1BA 0.9800

C1D—H1DB 0.9800 C1B—H1BB 0.9800

C1D—H1DC 0.9800 C1B—H1BC 0.9800

C2D—C3D 1.400 (6) C2B—C3B 1.392 (6)

C2D—C7D 1.420 (6) C2B—C7B 1.414 (6)

C3D—H3D 0.9500 C3B—H3B 0.9500

C3D—C4D 1.385 (8) C3B—C4B 1.367 (8)

C4D—H4D 0.9500 C4B—H4B 0.9500

C4D—C5D 1.395 (7) C4B—C5B 1.388 (8)

C5D—H5D 0.9500 C5B—H5B 0.9500

C5D—C6D 1.378 (7) C5B—C6B 1.387 (7)

C6D—H6D 0.9500 C6B—H6B 0.9500

C6D—C7D 1.401 (7) C6B—C7B 1.400 (7)

C7D—C8D 1.458 (6) C7B—C8B 1.449 (6)

C8D—H8D 0.9500 C8B—H8B 0.9500

C8D—C9D 1.319 (6) C8B—C9B 1.325 (6)

C9D—H9D 0.9500 C9B—H9B 0.9500

C9D—C10D 1.479 (6) C9B—C10B 1.477 (6)

C10D—C11D 1.484 (6) C10B—C11B 1.478 (6) C11D—C12D 1.372 (7) C11B—C12B 1.368 (7) C12D—C13D 1.419 (7) C12B—C13B 1.429 (7)

C13D—H13D 0.9500 C13B—H13B 0.9500

C13D—C14D 1.349 (8) C13B—C14B 1.387 (8)

C14D—H14D 0.9500 C14B—H14B 0.9500

C14C—S1C—C11C 92.4 (2) C14A—S1A—C11A 91.3 (3) C2C—O1C—C1C 119.0 (4) C2A—O1A—C1A 119.2 (4) O1C—C1C—H1CA 109.5 O1A—C1A—H1AA 109.5 O1C—C1C—H1CB 109.5 O1A—C1A—H1AB 109.5 O1C—C1C—H1CC 109.5 O1A—C1A—H1AC 109.5 H1CA—C1C—H1CB 109.5 H1AA—C1A—H1AB 109.5 H1CA—C1C—H1CC 109.5 H1AA—C1A—H1AC 109.5 H1CB—C1C—H1CC 109.5 H1AB—C1A—H1AC 109.5 O1C—C2C—C3C 125.2 (5) O1A—C2A—C3A 124.4 (5) O1C—C2C—C7C 114.9 (4) O1A—C2A—C7A 116.0 (4) C3C—C2C—C7C 119.9 (5) C3A—C2A—C7A 119.7 (5)

C2C—C3C—H3C 119.9 C2A—C3A—H3A 119.9

C4C—C3C—C2C 120.3 (5) C4A—C3A—C2A 120.1 (5)

C4C—C3C—H3C 119.9 C4A—C3A—H3A 119.9

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C5C—C4C—C3C 121.4 (5) C3A—C4A—C5A 121.0 (5)

C5C—C4C—H4C 119.3 C5A—C4A—H4A 119.5

C4C—C5C—H5C 120.6 C4A—C5A—H5A 120.6

C4C—C5C—C6C 118.8 (5) C6A—C5A—C4A 118.8 (5)

C6C—C5C—H5C 120.6 C6A—C5A—H5A 120.6

C5C—C6C—H6C 118.9 C5A—C6A—H6A 119.2

C7C—C6C—C5C 122.2 (5) C5A—C6A—C7A 121.5 (5)

C7C—C6C—H6C 118.9 C7A—C6A—H6A 119.2

C2C—C7C—C8C 118.6 (4) C2A—C7A—C8A 118.0 (4) C6C—C7C—C2C 117.5 (5) C6A—C7A—C2A 118.9 (4) C6C—C7C—C8C 123.9 (5) C6A—C7A—C8A 123.1 (5)

C7C—C8C—H8C 115.9 C7A—C8A—H8A 116.4

C9C—C8C—C7C 128.2 (5) C9A—C8A—C7A 127.2 (5)

C9C—C8C—H8C 115.9 C9A—C8A—H8A 116.4

C8C—C9C—H9C 120.2 C8A—C9A—H9A 120.6

C8C—C9C—C10C 119.5 (5) C8A—C9A—C10A 118.7 (4) C10C—C9C—H9C 120.2 C10A—C9A—H9A 120.6 O2C—C10C—C9C 121.6 (4) O2A—C10A—C9A 121.6 (4) O2C—C10C—C11C 117.8 (4) O2A—C10A—C11A 117.6 (4) C9C—C10C—C11C 120.6 (4) C9A—C10A—C11A 120.8 (4) C10C—C11C—S1C 113.6 (3) C10A—C11A—S1A 113.7 (3) C12C—C11C—S1C 110.2 (4) C12A—C11A—S1A 109.4 (4) C12C—C11C—C10C 136.1 (5) C12A—C11A—C10A 136.9 (4) C11C—C12C—Br1C 127.4 (4) C11A—C12A—Br1A 126.4 (4) C11C—C12C—C13C 113.0 (5) C11A—C12A—C13A 114.8 (5) C13C—C12C—Br1C 119.6 (4) C13A—C12A—Br1A 118.8 (4) C12C—C13C—H13C 123.9 C12A—C13A—H13A 124.5 C14C—C13C—C12C 112.3 (5) C14A—C13A—C12A 111.1 (5) C14C—C13C—H13C 123.9 C14A—C13A—H13A 124.5 S1C—C14C—H14C 123.9 S1A—C14A—H14A 123.2 C13C—C14C—S1C 112.2 (4) C13A—C14A—S1A 113.5 (4) C13C—C14C—H14C 123.9 C13A—C14A—H14A 123.2 C14D—S1D—C11D 92.0 (3) C14B—S1B—C11B 92.8 (3) C2D—O1D—C1D 119.1 (4) C2B—O1B—C1B 119.4 (4) O1D—C1D—H1DA 109.5 O1B—C1B—H1BA 109.5 O1D—C1D—H1DB 109.5 O1B—C1B—H1BB 109.5 O1D—C1D—H1DC 109.5 O1B—C1B—H1BC 109.5 H1DA—C1D—H1DB 109.5 H1BA—C1B—H1BB 109.5 H1DA—C1D—H1DC 109.5 H1BA—C1B—H1BC 109.5 H1DB—C1D—H1DC 109.5 H1BB—C1B—H1BC 109.5 O1D—C2D—C3D 123.7 (5) O1B—C2B—C3B 124.8 (5) O1D—C2D—C7D 115.7 (4) O1B—C2B—C7B 115.1 (4) C3D—C2D—C7D 120.6 (5) C3B—C2B—C7B 120.1 (5)

C2D—C3D—H3D 120.6 C2B—C3B—H3B 119.9

C4D—C3D—C2D 118.8 (5) C4B—C3B—C2B 120.3 (5)

C4D—C3D—H3D 120.6 C4B—C3B—H3B 119.9

C3D—C4D—H4D 119.4 C3B—C4B—H4B 119.4

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C5D—C4D—H4D 119.4 C5B—C4B—H4B 119.4

C4D—C5D—H5D 120.0 C4B—C5B—H5B 120.5

C6D—C5D—C4D 120.0 (5) C6B—C5B—C4B 118.9 (6)

C6D—C5D—H5D 120.0 C6B—C5B—H5B 120.6

C5D—C6D—H6D 119.6 C5B—C6B—H6B 119.2

C5D—C6D—C7D 120.7 (5) C5B—C6B—C7B 121.6 (5)

C7D—C6D—H6D 119.6 C7B—C6B—H6B 119.2

C2D—C7D—C8D 118.8 (4) C2B—C7B—C8B 119.2 (5) C6D—C7D—C2D 118.5 (4) C6B—C7B—C2B 117.9 (5) C6D—C7D—C8D 122.7 (5) C6B—C7B—C8B 122.9 (5)

C7D—C8D—H8D 115.7 C7B—C8B—H8B 115.7

C9D—C8D—C7D 128.6 (5) C9B—C8B—C7B 128.6 (5)

C9D—C8D—H8D 115.7 C9B—C8B—H8B 115.7

C8D—C9D—H9D 120.1 C8B—C9B—H9B 120.2

C8D—C9D—C10D 119.8 (4) C8B—C9B—C10B 119.6 (4) C10D—C9D—H9D 120.1 C10B—C9B—H9B 120.2 O2D—C10D—C9D 122.1 (4) O2B—C10B—C9B 121.9 (5) O2D—C10D—C11D 117.5 (4) O2B—C10B—C11B 118.1 (4) C9D—C10D—C11D 120.3 (4) C9B—C10B—C11B 120.0 (4) C10D—C11D—S1D 113.3 (3) C10B—C11B—S1B 113.0 (4) C12D—C11D—S1D 109.7 (4) C12B—C11B—S1B 109.7 (4) C12D—C11D—C10D 137.0 (5) C12B—C11B—C10B 137.3 (5) C11D—C12D—Br1D 127.0 (4) C11B—C12B—Br1B 127.1 (4) C11D—C12D—C13D 113.9 (5) C11B—C12B—C13B 114.3 (5) C13D—C12D—Br1D 119.0 (4) C13B—C12B—Br1B 118.6 (4) C12D—C13D—H13D 124.3 C12B—C13B—H13B 124.5 C14D—C13D—C12D 111.4 (5) C14B—C13B—C12B 111.0 (5) C14D—C13D—H13D 124.3 C14B—C13B—H13B 124.5 S1D—C14D—H14D 123.5 S1B—C14B—H14B 123.9 C13D—C14D—S1D 113.0 (4) C13B—C14B—S1B 112.2 (4) C13D—C14D—H14D 123.5 C13B—C14B—H14B 123.9

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Acta Cryst. (2015). E71, 965-971 Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C9C—H9C···Br1C 0.95 2.68 3.401 (5) 133 C9D—H9D···Br1D 0.95 2.69 3.405 (4) 133 C9A—H9A···Br1A 0.95 2.69 3.398 (5) 132 C9B—H9B···Br1B 0.95 2.68 3.401 (5) 133

(II) (2E)-1-(3-Bromothiophen-2-yl)-3-(3,4-dimethoxyphenyl)prop-2-en-1-one

Crystal data

C15H13BrO3S Mr = 353.22

Monoclinic, I2/a a = 13.4748 (7) Å

b = 8.3853 (3) Å

c = 25.0214 (9) Å

β = 93.957 (4)°

V = 2820.4 (2) Å3 Z = 8

F(000) = 1424

Dx = 1.664 Mg m−3

Cu Kα radiation, λ = 1.54184 Å Cell parameters from 2804 reflections

θ = 5.5–71.4°

µ = 5.40 mm−1 T = 173 K Irregular, yellow 0.32 × 0.28 × 0.22 mm

Data collection

Agilent Eos Gemini diffractometer

Radiation source: Enhance (Cu) X-ray Source Detector resolution: 16.0416 pixels mm-1 ω scans

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)

Tmin = 0.726, Tmax = 1.000

5523 measured reflections 2690 independent reflections 2399 reflections with I > 2σ(I)

Rint = 0.026

θmax = 71.4°, θmin = 3.5°

h = −13→16

k = −7→10

l = −30→23

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.074} wR(F2_{) = 0.187} S = 1.04 2690 reflections 183 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(Fo2_{) + (0.0864P)}2 _{+ 41.1386P]}

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max < 0.001

Δρmax = 3.38 e Å−3

Δρmin = −2.20 e Å−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm

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Acta Cryst. (2015). E71, 965-971

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

Br1 0.61968 (8) 0.91781 (8) 0.53629 (3) 0.0580 (3) S1 0.64474 (11) 0.66323 (16) 0.68963 (5) 0.0276 (3) O1 0.6334 (3) 0.3966 (4) 0.61923 (14) 0.0274 (8) O2 0.5945 (3) 0.6136 (4) 0.32362 (14) 0.0240 (8) O3 0.6189 (3) 0.3395 (4) 0.28114 (13) 0.0240 (8) C1 0.6314 (3) 0.5174 (6) 0.59246 (18) 0.0182 (9) C2 0.6360 (3) 0.6745 (6) 0.62051 (18) 0.0177 (9) C3 0.6336 (4) 0.8322 (6) 0.60615 (19) 0.0218 (10) C4 0.6394 (4) 0.9416 (7) 0.6490 (2) 0.0272 (11)

H4 0.6388 1.0542 0.6449 0.033*

C5 0.6460 (4) 0.8652 (7) 0.6967 (2) 0.0296 (12)

H5 0.6508 0.9182 0.7304 0.035*

C6 0.6245 (4) 0.5171 (6) 0.53382 (19) 0.0235 (10)

H6 0.6173 0.6159 0.5153 0.028*

C7 0.6282 (4) 0.3831 (6) 0.50554 (19) 0.0204 (10)

H7 0.6344 0.2862 0.5252 0.025*

C8 0.6235 (4) 0.3708 (6) 0.44730 (19) 0.0191 (9) C9 0.6359 (4) 0.2233 (6) 0.4232 (2) 0.0233 (10)

H9 0.6460 0.1312 0.4450 0.028*

C10 0.6339 (4) 0.2082 (6) 0.3679 (2) 0.0226 (10)

H10 0.6417 0.1060 0.3523 0.027*

C11 0.6207 (4) 0.3397 (6) 0.33556 (18) 0.0185 (9) C12 0.6083 (3) 0.4915 (5) 0.35916 (19) 0.0173 (9) C13 0.6105 (3) 0.5049 (6) 0.41371 (19) 0.0182 (9)

H13 0.6031 0.6071 0.4293 0.022*

C14 0.6252 (4) 0.1871 (6) 0.2557 (2) 0.0280 (11)

H14A 0.6236 0.2016 0.2168 0.042*

H14B 0.5688 0.1208 0.2647 0.042*

H14C 0.6876 0.1347 0.2682 0.042*

C15 0.5831 (5) 0.7695 (6) 0.3449 (2) 0.0299 (12)

H15A 0.5705 0.8455 0.3155 0.045*

H15B 0.6440 0.7999 0.3661 0.045*

H15C 0.5269 0.7704 0.3678 0.045*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2015). E71, 965-971

C4 0.033 (3) 0.021 (2) 0.028 (3) −0.002 (2) 0.001 (2) −0.006 (2) C5 0.032 (3) 0.032 (3) 0.024 (3) −0.001 (2) −0.001 (2) −0.011 (2) C6 0.036 (3) 0.019 (2) 0.015 (2) −0.001 (2) −0.0031 (19) 0.0007 (18) C7 0.026 (2) 0.019 (2) 0.015 (2) −0.0017 (19) −0.0029 (18) 0.0020 (18) C8 0.025 (2) 0.019 (2) 0.013 (2) −0.0018 (19) −0.0029 (17) −0.0012 (18) C9 0.038 (3) 0.012 (2) 0.019 (2) 0.000 (2) 0.001 (2) 0.0038 (18) C10 0.034 (3) 0.013 (2) 0.020 (2) 0.0013 (19) −0.0009 (19) −0.0029 (19) C11 0.026 (2) 0.015 (2) 0.014 (2) 0.0001 (18) 0.0000 (17) −0.0025 (18) C12 0.021 (2) 0.012 (2) 0.018 (2) 0.0017 (17) −0.0006 (16) 0.0016 (18) C13 0.024 (2) 0.013 (2) 0.017 (2) 0.0008 (18) −0.0012 (17) −0.0034 (18) C14 0.046 (3) 0.021 (3) 0.017 (2) 0.000 (2) 0.000 (2) −0.007 (2) C15 0.048 (3) 0.012 (2) 0.029 (3) 0.001 (2) −0.002 (2) 0.002 (2)

Geometric parameters (Å, º)

Br1—C3 1.887 (5) C7—H7 0.9500

S1—C2 1.728 (5) C7—C8 1.458 (7)

S1—C5 1.703 (6) C8—C9 1.391 (7)

O1—C1 1.213 (6) C8—C13 1.407 (7)

O2—C12 1.360 (6) C9—H9 0.9500

O2—C15 1.424 (6) C9—C10 1.388 (7)

O3—C11 1.360 (6) C10—H10 0.9500

O3—C14 1.433 (6) C10—C11 1.372 (7)

C1—C2 1.492 (7) C11—C12 1.417 (6)

C1—C6 1.464 (6) C12—C13 1.368 (7)

C2—C3 1.370 (7) C13—H13 0.9500

C3—C4 1.409 (7) C14—H14A 0.9800

C4—H4 0.9500 C14—H14B 0.9800

C4—C5 1.353 (8) C14—H14C 0.9800

C5—H5 0.9500 C15—H15A 0.9800

C6—H6 0.9500 C15—H15B 0.9800

C6—C7 1.331 (7) C15—H15C 0.9800

C5—S1—C2 92.8 (3) C8—C9—H9 119.4

C12—O2—C15 117.4 (4) C10—C9—C8 121.2 (4)

C11—O3—C14 116.7 (4) C10—C9—H9 119.4

O1—C1—C2 118.6 (4) C9—C10—H10 119.7

O1—C1—C6 123.3 (5) C11—C10—C9 120.5 (4)

C6—C1—C2 118.0 (4) C11—C10—H10 119.7

C1—C2—S1 114.8 (3) O3—C11—C10 125.6 (4) C3—C2—S1 108.3 (4) O3—C11—C12 115.1 (4) C3—C2—C1 136.8 (4) C10—C11—C12 119.3 (4) C2—C3—Br1 127.5 (4) O2—C12—C11 114.7 (4) C2—C3—C4 115.4 (5) O2—C12—C13 125.6 (4) C4—C3—Br1 117.0 (4) C13—C12—C11 119.6 (4)

C3—C4—H4 124.4 C8—C13—H13 119.2

C5—C4—C3 111.2 (5) C12—C13—C8 121.6 (4)

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Acta Cryst. (2015). E71, 965-971

S1—C5—H5 123.9 O3—C14—H14A 109.5

C4—C5—S1 112.2 (4) O3—C14—H14B 109.5

C4—C5—H5 123.9 O3—C14—H14C 109.5

C1—C6—H6 118.9 H14A—C14—H14B 109.5

C7—C6—C1 122.1 (5) H14A—C14—H14C 109.5

C7—C6—H6 118.9 H14B—C14—H14C 109.5

C6—C7—H7 116.9 O2—C15—H15A 109.5

C6—C7—C8 126.2 (5) O2—C15—H15B 109.5

C8—C7—H7 116.9 O2—C15—H15C 109.5

C9—C8—C7 119.8 (4) H15A—C15—H15B 109.5 C9—C8—C13 117.7 (4) H15A—C15—H15C 109.5 C13—C8—C7 122.4 (4) H15B—C15—H15C 109.5

Br1—C3—C4—C5 178.1 (4) C6—C1—C2—S1 −179.6 (4) S1—C2—C3—Br1 −177.5 (3) C6—C1—C2—C3 1.8 (8) S1—C2—C3—C4 0.6 (6) C6—C7—C8—C9 175.0 (5) O1—C1—C2—S1 0.3 (6) C6—C7—C8—C13 −2.4 (8) O1—C1—C2—C3 −178.2 (6) C7—C8—C9—C10 −178.7 (5) O1—C1—C6—C7 −5.5 (8) C7—C8—C13—C12 178.6 (4) O2—C12—C13—C8 178.8 (4) C8—C9—C10—C11 0.8 (8) O3—C11—C12—O2 1.3 (6) C9—C8—C13—C12 1.1 (7) O3—C11—C12—C13 −179.0 (4) C9—C10—C11—O3 179.0 (5) C1—C2—C3—Br1 1.1 (9) C9—C10—C11—C12 −0.5 (8) C1—C2—C3—C4 179.2 (5) C10—C11—C12—O2 −179.2 (4) C1—C6—C7—C8 −179.1 (5) C10—C11—C12—C13 0.5 (7) C2—S1—C5—C4 0.5 (5) C11—C12—C13—C8 −0.8 (7) C2—C1—C6—C7 174.4 (5) C13—C8—C9—C10 −1.1 (8) C2—C3—C4—C5 −0.2 (7) C14—O3—C11—C10 4.1 (7) C3—C4—C5—S1 −0.2 (6) C14—O3—C11—C12 −176.4 (4) C5—S1—C2—C1 −179.5 (4) C15—O2—C12—C11 −179.1 (4) C5—S1—C2—C3 −0.6 (4) C15—O2—C12—C13 1.3 (7)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C5—H5···O2i _{0.95 2.52 3.301 (6) 140}

C5—H5···O3i _{0.95 2.45 3.291 (6) 148}

C6—H6···Br1 0.95 2.59 3.361 (5) 139

C14—H14A···O1ii _{0.98 2.59 3.495 (6) 154}